Halogen Bonding Promotes Higher Dye-Sensitized Solar Cell Photovoltages

We report here an enhancement in photovoltage for dye-sensitized solar cells (DSSCs) where halogen-bonding interactions exist between a nucleophilic electrolyte species (I–) and a photo-oxidized dye immobilized on a TiO2 surface. The triarylamine-based dyes under investigation showed larger rate constants for dye regeneration (kreg) by the nucleophilic electrolyte species when heavier halogen substituents were positioned on the dye. The open-circuit voltages (VOC) tracked these kreg values. This analysis of a homologous series of dyes that differ only in the identity of two halogen substituents provides compelling evidence that the DSSC photovoltage is sensitive to kreg. This study also provides the first direct evidence that halogen-bonding interactions between the dye and the electrolyte can bolster DSSC performance.